JP2015017258A - Improved vinyl modifier composition and method for using said composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oxolanyl compound-containing composition which is more active when used as a vinyl content modifier in a polymerization reaction.SOLUTION: The 2,2-di(2-tetrahydrofuryl)propane in the figure containing at least 52 wt.% of a meso-isomer exhibits high activity as a 1,2-vinyl content modifier in polymerizing diene monomers. (R1 and R2 are methyl groups; and R3 to R5 are -H.)

Description

  Embodiments of the present invention include an oxolanyl compound-containing composition comprising a specific amount of a meso-isomer of one or more oxolanyl compounds of a specific structure, and the use of such a composition as a vinyl content modifier in a polymerization process. About.

  In the preparation of (co) polymers having a 1,2-microstructure of between 10 and 95% from a monomer system comprising at least one conjugated diene monomer, the oligomeric oxolanyl compound is a microstructure (1,2-vinyl containing Amount) has been used as a modifier. Some of these oxolanyl compounds have at least two chiral centers, whereby there are D, L and meso stereoisomers. Commercially available compositions of oxolanyl compounds such as 2,2-di (2-tetrahydrofuryl) propane contain a mixture of about 50% D, L isomer and about 50% meso isomer.

式中、Ｒ_１およびＲ_２は、独立して、水素またはアルキル基であり、−ＣＲ_１Ｒ_２−における炭素原子の合計数は、１〜９であり；Ｒ_３、Ｒ_４およびＲ_５は、独立して、−Ｈまたは−Ｃ_ｎＨ_２ｎ＋１であり、ｎ＝１〜６である。その組成物は、少なくとも１種のオキソラニル化合物のメソ−異性体を少なくとも５２重量％含む。 Embodiments disclosed herein relate to oxolanyl compound-containing compositions that include specific amounts of meso-isomers of one or more oxolanyl compounds of a specific structure. The at least one oxolanyl compound present in the composition is selected from the following group:

Wherein R ₁ and R ₂ are independently hydrogen or an alkyl group, and the total number of carbon atoms in —CR ₁ R ₂ — is 1-9; R ₃ , R ₄ and R ₅ are it is independently -H or _-C n _{H 2n + 1,} a n = 1 to 6. The composition comprises at least 52% by weight of the meso-isomer of at least one oxolanyl compound.

式中、Ｒ_１およびＲ_２は、独立して、水素またはアルキル基であり、−ＣＲ_１Ｒ_２−における炭素原子の合計数は、１〜９であり；Ｒ_３、Ｒ_４およびＲ_５は、独立して、−Ｈまたは−Ｃ_ｎＨ_２ｎ＋１であり、ｎ＝１〜６である。その組成物は、少なくとも１種のオキソラニル化合物のメソ−異性体を少なくとも５２重量％含む。 An additional embodiment is a polymerization process for the production of a polydiene polymer comprising the step of polymerizing at least one conjugated diene monomer in the presence of a composition comprising at least one oxolanyl compound selected from the following group: including:

Wherein R ₁ and R ₂ are independently hydrogen or an alkyl group, and the total number of carbon atoms in —CR ₁ R ₂ — is 1-9; R ₃ , R ₄ and R ₅ are it is independently -H or _-C n _{H 2n + 1,} a n = 1 to 6. The composition comprises at least 52% by weight of the meso-isomer of at least one oxolanyl compound.

  An additional embodiment includes a relatively high temperature polymerization process comprising polymerizing 1,3-butadiene in the presence of the oxolanyl compound 2,2-di (2-tetrahydrofuryl) propane, wherein the oxolanyl compound is , Containing at least 52% by weight of the meso-isomer. Such a process produces a polydiene polymer with a vinyl content between 10 and 65% and involves the use of an organolithium anionic initiator and is carried out at a temperature between 85 ° C and 120 ° C.

2 is a graph showing the effect of DTHP concentration (and meso content) on the 1,2-vinyl content of polybutadiene. It is a graph which shows the effect of the density | concentration (and meso content) of DTHP with respect to the 1, 2- vinyl content of a styrene-butadiene copolymer. It is ¹ H-NMR of meso-2,2-ditetrahydrofurylpropane. It is ¹ H-NMR of D, L-2,2-ditetrahydrofurylpropane. 2 is a graph showing the effect of the meso content of 2,2-ditetrahydrofurylpropane (at a constant 2,2-ditetrahydrofurylpropane concentration) on the 1,2-vinyl content of polybutadiene. FIG. 5 is a graph showing the polymerization rate of butadiene in the presence of 99.8% 2,2-ditetrahydrofurylpropane meso and 49.7% 2,2-ditetrahydrofurylpropane meso.

DETAILED DESCRIPTION The present disclosure provides an oxolanyl compound-containing composition comprising a specific amount of a meso-isomer of one or more oxolanyl compounds of a specific structure, and the use of such a composition as a vinyl content modifier in a polymerization process. About. The meso-isomer is more active when used as a vinyl content modifier in a polymerization reaction than a mixture of D-form, L-form and meso-form which are commercially available and used conventionally. , Was found unexpectedly. Due to the improved activity of the meso-isomer, the same results as commercially available mixtures of D, L and meso isomers can be achieved with the use of relatively little oxolanyl compound. Commercially available compositions of oxolanyl compounds such as 2,2-di (2-tetrahydrofuryl) propane have about 50% (ie, 50% + /-1%) D-form, L-form isomer, and about Contains a mixture with 50% (ie 50% + / − 1%) meso isomers.

式中、Ｒ_１およびＲ_２は、独立して、水素またはアルキル基であり、−ＣＲ_１Ｒ_２−における炭素原子の合計数は、１〜９であり；Ｒ_３、Ｒ_４およびＲ_５は、独立して、−Ｈまたは−Ｃ_ｎＨ_２ｎ＋１であり、ｎ＝１〜６である。組成物は、少なくとも１種のオキソラニル化合物のメソ−異性体を少なくとも５２重量％含み、残りはＤ形およびＬ形立体異性体を含む。他の実施態様では、組成物は、メソ−異性体を、少なくとも５５重量％、６０重量％、少なくとも７５重量％、少なくとも９０重量％または１００重量％含む。いくつかの実施態様では、組成物は、１種のみのオキソラニル化合物を含み、他の実施態様では、組成物は、２種、３種、または３種以上の異なるオキソラニル化合物を含む。いくつかの実施態様では、少なくとも１種のオキソラニル化合物は、２，２−ジ（２−テトラヒドロフリル）プロパンを含む。 Embodiments disclosed herein relate to oxolanyl compound-containing compositions comprising at least 52% by weight of meso-isomers of one or more oxolanyl compounds. The at least one oxolanyl compound is selected from the following group:

Wherein R ₁ and R ₂ are independently hydrogen or an alkyl group, and the total number of carbon atoms in —CR ₁ R ₂ — is 1-9; R ₃ , R ₄ and R ₅ are it is independently -H or _-C n _{H 2n + 1,} a n = 1 to 6. The composition comprises at least 52% by weight of the meso-isomer of at least one oxolanyl compound, with the remainder comprising the D and L stereoisomers. In other embodiments, the composition comprises at least 55%, 60%, at least 75%, at least 90% or 100% by weight of the meso-isomer. In some embodiments, the composition includes only one oxolanyl compound, and in other embodiments, the composition includes two, three, or more than two different oxolanyl compounds. In some embodiments, the at least one oxolanyl compound comprises 2,2-di (2-tetrahydrofuryl) propane.

  In some embodiments, the composition comprising at least one oxolanyl compound selected from the specific group described above is obtained by known techniques such as column chromatography or fractional distillation, such as D-form, L-form and meso-form of the oxolanyl compound. It may be a purified mixture resulting from the separation of body mixtures. It is specifically contemplated that other separation techniques, now known and developed in the future, may be used to provide compositions containing a particular amount of meso-isomers of at least one oxolanyl compound. In other embodiments, the meso-isomer may be preferentially produced during the synthesis of at least one oxolanyl compound.

式中、Ｒ_１およびＲ_２は、独立して、水素またはアルキル基であり、−ＣＲ_１Ｒ_２−における炭素原子の合計数は、１〜９であり；Ｒ_３、Ｒ_４およびＲ_５は、独立して、−Ｈまたは−Ｃ_ｎＨ_２ｎ＋１であり、ｎ＝１〜６である。後述するように、種々の１，３−ジエンモノマーを、その方法において用いてもよい。組成物は、少なくとも１種のオキソラニル化合物のメソ−異性体を少なくとも５２重量％含み、残りはＤ形およびＬ形立体異性体を含む。他の実施態様では、組成物は、メソ−異性体を、少なくとも５５重量％、６０重量％、少なくとも７５重量％、少なくとも９０重量％または１００重量％含む。いくつかの実施態様では、組成物は、１種のみのオキソラニル化合物を含み、他の実施態様では、組成物は、２種、３種、または３種以上の異なるオキソラニル化合物を含む。いくつかの実施態様では、少なくとも１種のオキソラニル化合物は、２，２−ジ（２−テトラヒドロフリル）プロパンを含む。 An additional embodiment is a polymerization process for the production of a polydiene polymer comprising the step of polymerizing at least one conjugated diene monomer in the presence of a composition comprising at least one oxolanyl compound selected from the following group: including:

Wherein R ₁ and R ₂ are independently hydrogen or an alkyl group, and the total number of carbon atoms in —CR ₁ R ₂ — is 1-9; R ₃ , R ₄ and R ₅ are it is independently -H or _-C n _{H 2n + 1,} a n = 1 to 6. As described below, various 1,3-diene monomers may be used in the method. The composition comprises at least 52% by weight of the meso-isomer of at least one oxolanyl compound, with the remainder comprising the D and L stereoisomers. In other embodiments, the composition comprises at least 55%, 60%, at least 75%, at least 90% or 100% by weight of the meso-isomer. In some embodiments, the composition includes only one oxolanyl compound, and in other embodiments, the composition includes two, three, or more than two different oxolanyl compounds. In some embodiments, the at least one oxolanyl compound comprises 2,2-di (2-tetrahydrofuryl) propane.

  The polymerization process may optionally include copolymerization of at least one conjugated diene monomer and at least one additional monomer including, but not limited to, at least one vinyl aromatic monomer. In the method, as described later, various vinyl aromatic monomers may be used. The resulting polydiene copolymer may take various forms including, but not limited to, random copolymers and block copolymers. In some embodiments, the copolymer is a block copolymer of polybutadiene, polystyrene, and optionally polyisoprene. In certain embodiments, the (co) polymer is hydrogenated or partially hydrogenated.

The block copolymer can include at least one polyvinyl aromatic block and at least one polydiene block. In one embodiment, the polydiene block is characterized by a relatively high vinyl content. In one or more embodiments, the block copolymer is defined by Formula I below:
α-VD-ω '(I)
Where V is a polyvinyl aromatic block, D is a polydiene block, α and ω ′ are each independently a hydrogen atom, a functional group, or a polymer segment or polymer block, and D is Characterized by a vinyl content of at least 50%.

  In one or more embodiments, the polyvinyl aromatic block comprises three or more partial units derived from the polymerization of vinyl aromatic monomers. In one or more embodiments, the functional group includes an organic or inorganic moiety that includes at least one heteroatom. In one or more embodiments, the polymerized segment comprises a homopolymer or a copolymer.

  In one or more embodiments, D of Formula I is at least 10%, in other embodiments at least 50%, in other embodiments at least 55%, in other embodiments at least 60%, in other embodiments at least 65%, in other embodiments at least 70%, in other embodiments at least 75%, in other embodiments at least 80%, and in other embodiments at least 85% vinyl content (ie 1,2- Characterized by the percentage of sub-units located in the microstructure). In these or other embodiments, D of Formula I is less than 100%, in other embodiments less than 95%, in other embodiments less than 90%, in other embodiments less than 85%, and other implementations. Embodiments are characterized by a vinyl content of less than 80%. Vinyl content may be determined by proton NMR and, as reported herein, is a subunit located in a 1,2-microstructure based on the sum of the subunits derived from the polymerization of the conjugated diene monomer. The percentage.

  In one or more embodiments, the D block of Formula I is at least 250 derived from the polymerization of conjugated diene monomers, in other embodiments at least 350, in other embodiments at least 450, and in other embodiments at least 550. Including partial units. In these or other embodiments, the D block of formula I is less than 800 derived from the polymerization of conjugated diene monomers, in other embodiments less than 750, in other embodiments less than 700, in other embodiments 650. Less, in other embodiments less than 600 sub-units.

  In one or more embodiments, the V block copolymer of Formula I is at least 50 derived from the polymerization of vinyl aromatic monomers, in other embodiments at least 120, in other embodiments at least 145, other embodiments. At least 160, in other embodiments at least 180, in other embodiments at least 200, and in other embodiments at least 225 sub-units. In these or other embodiments, the V block of Formula I is less than 400 derived from the polymerization of vinyl aromatic monomers, in other embodiments less than 350, in other embodiments less than 325, in other embodiments. Less than 300, and in other embodiments less than 280 partial units.

  In one or more embodiments, the block copolymer defined by Formula I is characterized by a low level of tapering, which may also be referred to as randomness between blocks of the polymer chain. In other words, for example, the vinyl aromatic block (eg, polystyrene block) of the block copolymer is limited, if any, derived from conjugated dienes (eg, 1,3-butadiene) within the block. With a number of sub-units. For purposes of this specification, tapering refers to the level or amount (in moles) of the subunits present in a given block as an impurity in the block (eg, styrene subunits in a polybutadiene block). In one or more embodiments, the block copolymer block defined by Formula I is less than 5% in any given block of the block copolymer, less than 3% in other embodiments, etc. This embodiment includes less than 1% taper and in other embodiments less than 0.5% taper. In these or other embodiments, the block copolymer block defined by Formula I has substantially no tapering, which is less than or equal to a taper that has no appreciable effect on the block copolymer. Includes rings. In one or more embodiments, the block copolymer block defined by Formula I has no tapering.

In one or more embodiments, α is a diene block derived from the polymerization of a diene monomer, and thus the block copolymer can be defined by the following Formula II:
dVD-ω '
Where d is a polydiene block derived from the polymerization of a diene monomer, V, D and ω ′ are as defined above for Formula I, and D and d are at least 50% vinyl content Is characterized by

  In one or more embodiments, d of formula II is at least 10%, in other embodiments at least 50%, in other embodiments at least 55%, in other embodiments at least 60%, in other embodiments at least 65%, in other embodiments at least 70%, in other embodiments at least 75%, in other embodiments at least 80%, in other embodiments at least 85% vinyl content (ie 1,2-micro Characterized by the percentage of partial units located in the structure). In these or other embodiments, D is less than 100%, in other embodiments less than 95%, in other embodiments less than 90%, in other embodiments less than 85%, and in other embodiments 80. Characterized by a vinyl content of less than%.

  In one or more embodiments, d of formula II is at least 10, derived from the polymerization of conjugated diene monomers, in other embodiments at least 40, in other embodiments at least 60, in other embodiments at least 80, etc. In some embodiments, at least 100, and in other embodiments, at least 120 partial units. In these or other embodiments, d of formula II is less than 500 derived from the polymerization of conjugated diene monomers, in other embodiments less than 350, in other embodiments less than 250, in other embodiments less than 200. , In other embodiments less than 180, in other embodiments less than 160, and in other embodiments less than 120 sub-units.

  In one or more embodiments, the block copolymer block defined by Formula II is less than 5% in any given block of the block copolymer, less than 3% in other embodiments, etc. This embodiment includes less than 1% taper and in other embodiments less than 0.5% taper. In these or other embodiments, the block copolymer block defined by Formula II has substantially no tapering, which is less than or equal to a taper that has no appreciable effect on the block copolymer. Includes rings. In one or more embodiments, the block copolymer block defined by Formula III has no tapering.

In one or more embodiments, the block copolymer can be defined by the following Formula III:
α−V ^o −DV′−ω ′
Where each V is independently a polyvinyl aromatic block, D is a polydiene block, and α and ω ′ are each independently a hydrogen atom, a functional group, or a polymer segment or polymer block. And D is characterized by a vinyl content of at least 50%.

  In one or more embodiments, D of Formula III is at least 10%, in other embodiments at least 50%, in other embodiments at least 55%, in other embodiments at least 60%, in other embodiments at least 65%, in other embodiments at least 70%, in other embodiments at least 75%, in other embodiments at least 80%, in other embodiments at least 85% vinyl content (ie 1,2-micro Characterized by the percentage of partial units located in the structure). In these or other embodiments, D is less than 100%, in other embodiments less than 95%, in other embodiments less than 90%, in other embodiments less than 85%, and in other embodiments 80. Characterized by a vinyl content of less than%.

  In one or more embodiments, D of formula III is a moiety of at least 250, in other embodiments at least 350, in other embodiments at least 450, in other embodiments at least 550 derived from polymerization of conjugated diene monomers. Includes units. In these or other embodiments, the D block of Formula III is less than 800, in other embodiments less than 750, in other embodiments less than 700, in other embodiments 650 derived from the polymerization of conjugated diene monomers. Less, in other embodiments less than 600 sub-units.

In one or more embodiments, the V ^o block and V ′ block of formula III are each independently at least 25 derived from the polymerization of vinyl aromatic monomers, in other embodiments at least 60, in other embodiments At least 75, in other embodiments at least 80, in other embodiments at least 90, in other embodiments at least 100, and in other embodiments at least 115 subunits. In these or other embodiments, the V ^o and V ′ blocks are each independently less than 200 derived from the polymerization of vinyl aromatic monomers, in other embodiments less than 175, in other embodiments 160. Less than, in other embodiments less than 150, and in other embodiments less than 140 sub-units.

In one or more embodiments, the ratio of V ^o subunit to V ′ subunit is at least 0.2: 1, in other embodiments at least 0.4: 1, in other embodiments at least 0.6: 1. , In other embodiments at least 0.8: 1, in other embodiments at least 0.9: 1, and in other embodiments at least 0.95: 1. In, the ratio V 'partial unit of V ^o partial unit these or other embodiments, 4: less than 1, in other embodiments 3: less than 1, in other embodiments less than 2: 1, other implementations In embodiments, less than 1.5: 1, in other embodiments less than 1.1: 1, and in other embodiments less than 1.05: 1. In one or more embodiments, the ratio of V ^o subunit to V ′ subunit is about 1: 1.

  In one or more embodiments, the block copolymer block defined by Formula III is less than 5% in any given block of the block copolymer, less than 3% in other embodiments, other This embodiment includes less than 1% taper and in other embodiments less than 0.5% taper. In these or other embodiments, the block copolymer block defined by Formula III has substantially no tapering, which is less than or equal to a taper that has no appreciable effect on the block copolymer. Includes rings. In one or more embodiments, the block copolymer block defined by Formula III has no tapering.

In one or more embodiments, α in formula III is a diene block, and thus the block copolymer may be defined by the following formula IV:
dV ^o −DV′−ω ′
Where d is a polydiene block, V ^o , V ′, D, and ω ′ are as defined above for Formula III, and D and d are characterized by a vinyl content of at least 50%. It is done.

  In one or more embodiments, d of formula IV is at least 10%, in other embodiments at least 50%, in other embodiments at least 55%, in other embodiments at least 60%, in other embodiments at least 65%, in other embodiments at least 70%, in other embodiments at least 75%, in other embodiments at least 80%, and in other embodiments at least 85% vinyl content (ie 1,2- Characterized by the percentage of sub-units located in the microstructure). In these or other embodiments, d of formula IV is less than 100%, in other embodiments less than 95%, in other embodiments less than 90%, in other embodiments less than 85%, and other implementations. Embodiments are characterized by a vinyl content of less than 80%. In one or more embodiments, d of formula IV is at least 10, derived from the polymerization of conjugated diene monomers, in other embodiments at least 40, in other embodiments at least 60, and in other embodiments at least 80, Other embodiments include at least 100 and in other embodiments at least 120 subunits. In these or other embodiments, d of formula IV is less than 500 derived from the polymerization of conjugated diene monomers, in other embodiments less than 350, in other embodiments less than 250, in other embodiments less than 200. , In other embodiments less than 180, in other embodiments less than 160, and in other embodiments less than 120 sub-units.

  In one or more embodiments, the peak molecular weight (Mp) of the overall block copolymer is at least 40 kg / mol, in other embodiments 50 kg / mol, in other embodiments 60 kg / mol, and in other embodiments 70 kg. / Mol. In these or other embodiments, the overall peak molecular weight (Mp) of the block copolymer is less than 150 kg / mol, in other embodiments less than 125 kg / mol, in other embodiments less than 100 kg / mol, and others In this embodiment, it may be less than 90 kg / mol.

  In one or more embodiments, the overall vinyl content of the block copolymer is at least 10%, in other embodiments at least 50%, in other embodiments at least 55%, in other embodiments at least 60%, It may be at least 65% in other embodiments, at least 70% in other embodiments, at least 75% in other embodiments, at least 80% in other embodiments, and at least 85% in other embodiments. . In these or other embodiments, d of formula IV is less than 100%, in other embodiments less than 95%, in other embodiments less than 90%, in other embodiments less than 85%, and other implementations. Embodiments are characterized by a vinyl content of less than 80%. As those skilled in the art will appreciate, the overall vinyl content of the block copolymer can be adjusted by adjusting the vinyl content of a particular diene block. For example, in block copolymers defined by Formulas II and IV, the vinyl content of the d block can be increased without necessarily resulting in a corresponding increase in the D block, resulting in an overall vinyl content of the block copolymer. Act on the increase.

  In one or more embodiments, the block copolymer block defined by Formula IV is less than 5% in any given block of the block copolymer, less than 3% in other embodiments, etc. This embodiment includes less than 1% taper and in other embodiments less than 0.5% taper. In these or other embodiments, the block copolymer block defined by Formula IV has substantially no tapering, which is less than or equal to a taper that has no appreciable effect on the block copolymer. Includes rings. In one or more embodiments, the block copolymer block defined by Formula IV has no tapering.

  In one or more embodiments, the block copolymer can be synthesized using an anionic polymerization method. In one or more embodiments, the living polymer comprises an anionically polymerized polymer (ie, a polymer prepared by an anionic polymerization method). An anionically polymerized living polymer may be formed by reacting an anionic initiator with several unsaturated monomers to grow a polymeric structure. Throughout the formation and growth of the polymer, its macromolecular structure may be anionic or “living”. New batches of monomer that are subsequently added to the reaction can be added to the living ends of the existing chains, increasing the degree of polymerization. Living polymers thus include polymerized moieties having living or reactive ends. Anionic polymerization is further described in George Odian's Principles of Polymerization, Chapter 5 (3rd edition, 1991), or Panek's 94J. Am. Chem. Soc., 8768 (1972), incorporated herein by reference. The

  In one or more embodiments, block copolymers may be prepared by sequential addition of separate monomers, resulting in various blocks. For example, a vinyl aromatic monomer can be fed and polymerized to form a living polyvinyl aromatic living polymer chain. The conjugated diene monomer may be fed after the vinyl aromatic monomer is consumed or substantially consumed. The conjugated diene monomer is added to the living polyvinyl aromatic chain to form a polydiene block connected to the living polyvinyl aromatic chain. After the diene monomer has been consumed or substantially consumed, additional monomers may be added to form other blocks linked to the copolymer. For example, vinyl aromatic monomers may be supplied to form other vinyl aromatic blocks. This process may be continued until the living polymer is deactivated (eg, protonated).

  The method can be initiated by using an anionic polymerization initiator, but other means may be used to initiate the polymerization, as those skilled in the art will appreciate.

  In order to achieve the desired vinyl content of the polydiene block, the polymerization of the diene monomer should be performed in the presence of the oxolanyl compound-containing composition described herein while maintaining the polymerization medium below a certain threshold temperature. Can do.

  In one or more embodiments, the polymerization of the polydiene blocks (ie, D and d) may include an initial batch temperature (ie, the temperature of the polymerization medium at the start of polymerization of the diene monomer) of less than 30 ° C., in other embodiments This is done by setting it below 25 ° C, in other embodiments below 20 ° C, in other embodiments below 15 ° C, and in other embodiments below 12 ° C. In these or other embodiments, the initial batch temperature may be set to greater than −10 ° C., in other embodiments greater than 0 ° C., and in other embodiments greater than 5 ° C.

  In one or more embodiments, the temperature of the polymerization medium during polymerization of the conjugated diene monomer (ie, during formation of the polydiene block D or d) is such that the peak polymerization temperature is less than 60 ° C, in other embodiments 55 ° C. Less than 50 ° C in other embodiments, less than 48 ° C in other embodiments, less than 45 ° C in other embodiments, less than 40 ° C in other embodiments, less than 35 ° C in other embodiments, and other In embodiments, it is kept to achieve less than 30 ° C. As those skilled in the art will appreciate, the initial batch temperature can be controlled by employing several methods, as well as by a combination of these methods, as well as the peak polymerization temperature. For example, the jacket temperature may be adjusted, a reflux condenser may be used, a specific solvent may be selected, and the polymerization solids concentration may be adjusted. Use of bis-oxolanylpropane and its oligomers as vinyl modifiers in the production of block copolymers advantageously provides the advantages of relatively high peak polymerization temperatures and relatively high vinyl polydiene blocks. Was discovered unexpectedly. As those skilled in the art will appreciate, this is very advantageous because it can produce block copolymers with relatively fast polymerization to produce relatively large amounts of polymer, thereby making the block Polymer production becomes commercially viable. For example, in one or more embodiments, polymerization of the D block or block of one or more block copolymers (eg, polydiene block) is at least 18 ° C, in other embodiments at least 20 ° C, other It is possible to achieve peak polymerization temperatures of at least 23 ° C in embodiments, at least 25 ° C in other embodiments, at least 27 ° C in other embodiments, and at least 30 ° C in other embodiments. In these or other embodiments, particularly when the block copolymer comprises a diene block d (such as Formula II or IV), the advantage is that the peak polymerization temperature is lower than that maintained during polymerization of the D block. It was unexpectedly discovered that it can be achieved by holding For example, in one or more embodiments, the peak polymerization temperature achieved during polymerization of the d block is at least 5 ° C, in other embodiments at least 8 ° C, in other embodiments at least 10 ° C, other embodiments. At least 12 ° C, in other embodiments at least 15 ° C, and in other embodiments at least 18 ° C. In these or other embodiments, the peak polymerization temperature achieved during polymerization of the d block is less than 35 ° C., in other embodiments less than 30 ° C., in other embodiments less than 27 ° C., other embodiments At less than 25 ° C, and in other embodiments less than 22 ° C.

  In one or more embodiments, by maintaining the solids concentration of the polymerization medium at a specified concentration during formation of the polydiene block defined by D (in the above formula), a commercially viable rate and amount It has been unexpectedly found to be advantageous in that an advantageous product is produced. For example, in one or more embodiments, during formation of the D block, the solids content of the polymerization medium is at least 6%, in other embodiments at least 7%, in other embodiments at least 8%, other embodiments. At least 9%, in other embodiments at least 10%, in other embodiments at least 11%, and in other embodiments at least 12%. In these or other embodiments, during the formation of the D block, the solids content of the polymerization medium is less than 22%, in other embodiments less than 20%, in other embodiments less than 18%, other embodiments. At less than 15% and in other embodiments less than 13%. Similarly, during formation of the polydiene block defined by d (in the above formula), an advantageous product at a commercially feasible rate and quantity by keeping the solids concentration of the polymerization medium at a specific concentration. Unexpectedly found that there is an advantage in generating. For example, in one or more embodiments, during formation of the d block, the solids content of the polymerization medium is at least 0.5%, in other embodiments at least 1%, in other embodiments at least 2%, other In embodiments, it is kept at a value of at least 3%, in other embodiments at least 4%, in other embodiments at least 5%, and in other embodiments at least 6%. In these or other embodiments, during the formation of the d block, the solids content of the polymerization medium is less than 8%, in other embodiments less than 7%, in other embodiments less than 6%, other embodiments At less than 5% and in other embodiments at less than 4%.

  The polymerization may be performed in a batch process, a continuous process, or a semi-continuous process. In one or more embodiments, the polymerization is conducted at a pressure of from about 0.1 atmosphere to about 50 atmospheres, in other embodiments from about 0.5 atmosphere to about 20 atmospheres, and in other embodiments from about 1 atmosphere to about 10 atmospheres. The conditions may be controlled so that In these or other embodiments, the polymerization mixture may be kept under anaerobic conditions.

  As those skilled in the art will appreciate, the solids content and peak polymerization temperature of the polymerization medium achieved during the formation of the vinyl aromatic block V maximizes efficiency without affecting the vinyl content of the polydiene block. Can be adjusted to achieve.

  In one or more embodiments, the production of the block copolymer occurs at a technically useful production rate. For example, in one or more embodiments, when working with the solid content provided herein for polydiene blocks, a conversion of at least 90% of the polymerized monomer is at least 8 hours, in other embodiments It is achieved within at least 6 hours, in other embodiments at least 5 hours, in other embodiments at least 4 hours, and in other embodiments within at least 3 hours. In one or more embodiments, the overall polymerization rate of the monomer is achieved at a technically useful level; for example, at least 90% of the charged monomer when operated under the conditions provided herein. Conversion rates of at least 92% in other embodiments, at least 95% in other embodiments, at least 97% in other embodiments, and at least 99% in other embodiments.

  In one or more embodiments, a quenching agent may be added to the polymerization mixture to inactivate the remaining living polymer chains. Antioxidants may be added with or without the addition of the quenching agent. The amount of antioxidant used can be, for example, in the range of 0.2% to 1% by weight of the polymerization product. In one or more embodiments, functionalizing agents or coupling agents may be used in place of or with the quenching agent.

  When the polymerization mixture is deactivated, the polymerization product may be recovered from the polymerization mixture by using conventional desorption and drying methods known in the art. For example, the polymer may be recovered by subjecting the polymer cement to steam demelting and then drying the resulting polymer crumb in a hot air tunnel. Alternatively, the polymer may be recovered by directly drying the polymer cement. The content of volatile substances in the dried polymer can be less than 1% by weight of the polymer, in other embodiments less than 0.5% by weight.

  The properties of the resulting (co) polymer can vary greatly by using techniques well known in the art. The relative amounts of at least one conjugated diene monomer and at least one vinyl aromatic monomer present in the resulting (co) polymer can vary greatly. In some embodiments, the amount of at least one conjugated diene monomer present in the co (polymer) ranges from 100% to 1% by weight. In other embodiments, the amount of the at least one conjugated diene monomer ranges from 100 wt% to 10 wt%, 100 wt% to 15 wt%, 100 wt% to 20 wt%, 90 wt% to 60 wt%. .

  The polydiene (co) polymer resulting from the polymerization process can take various vinyl contents (1,2-vinyl content), including but not limited to, generally in the range of 10% or more and less than 100%. In some embodiments (such as relatively high temperature processes), the resulting polydiene (co) polymer has a vinyl content of 10% to 65%, at least 45%, 45% to 90%, at least 60%, Or 60% to 90%, or less than 100%. In other embodiments, the resulting polydiene (co) polymer has a vinyl content of at least 50%, at least 55%, at least 70%, at least 75%, at least 80%, at least 85%, less than 95%, 90% %, Less than 85% or less than 80%.

  The polydiene (co) polymers obtained from the polymerization methods described herein can take various Mw (weight average molecular weight) and Mn (number average molecular weight). The (co) polymer is calibrated with polystyrene standards and measured using gel permeation chromatography (GPC) adjusted with the Mark-Houwink constant of the polymer, preferably 50-2,000 kg / mol, preferably It has a number average molecular weight of 50-300 kg / mol. The (co) polymer molecular weight distribution (Mw / Mn) (also known as polydispersity) is preferably less than 2, more preferably less than 1.5, and even more preferably less than 1.3. .

  In some embodiments, the polymerization process also includes the use of at least one organometallic anionic initiator. In the method, as described later, various organometallic anionic initiators may be used.

  In some embodiments, the meso-isomer of the oxolanyl compound is used in a specific molar ratio with respect to the organometallic anionic initiator. Such ratios include, but are not limited to, 0.01: 10 to 0.05: 5, 0.1: 1, 0.1: 0.7, and 1: 1 (or 0, .001: 1, 0.01: 1, 0.1: 1, 0.14: 1, and 1: 1 including 0.001: 1 to 0.14: 1).

  Usually, the polymerization process is carried out using conditions and reactants well known to those skilled in the art. Examples of such conditions and reactants are set forth below and should be construed as illustrative and not limiting in any way.

  Conjugated dienes that can be used in the polymerization method are not limited to these, but include 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2 -Ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene. A mixture of two or more conjugated dienes may be used for the copolymerization. Preferred conjugated dienes are 1,3-butadiene, isoprene, 1,3-pentadiene, and 1,3-hexadiene.

  Aromatic vinyl monomers that may be used in the polymerization process include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, and vinylnaphthalene.

  Anionic polymerization initiators used in the polymerization method include, but are not limited to, organic sodium, organic potassium, organic magnesium, organic tin-lithium, and organic lithium initiator. As an example of such an initiator, an organolithium compound useful in the polymerization of 1,3-diene monomers is a hydrocarbyl lithium compound having the formula RLi, where R is 1-20 carbon atoms, Preferably it represents a hydrocarbyl group containing 2 to 8 carbon atoms. The hydrocarbyl group is preferably an aliphatic group, but the hydrocarbyl group may be alicyclic or aromatic. Aliphatic groups may be primary, secondary, or tertiary groups, with primary and secondary groups being optimal. Examples of aliphatic hydrocarbyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-amyl, sec-amyl, n-hexyl, sec-hexyl, n-heptyl, Includes n-octyl, n-nonyl, n-dodecyl, and octadecyl. The aliphatic group may contain unsaturation such as allyl and 2-butenyl. Examples of cycloalkyl groups include cyclohexyl, methylcyclohexyl, ethylcyclohexyl, cycloheptyl, cyclopentylmethyl, and methylcyclopentylethyl. Examples of aromatic hydrocarbyl groups include phenyl, tolyl, phenylethyl, benzyl, naphthyl, phenylcyclohexyl and the like.

  Specific examples of organolithium compounds useful as anionic initiators in polymerization include, but are not limited to, n-butyllithium, n-propyllithium, iso-butyllithium, tert-butyllithium, tributyltinlithium 5,268,439), amyl-lithium, cyclohexyl lithium and the like. Other suitable organolithium compounds for use as anionic initiators are well known to those skilled in the art. Mixtures of different lithium initiator compounds can also be used. Typical and preferred organo-lithium initiators are n-butyllithium, tributyltinlithium, and “in situ” prepared lithium hexamethyleneimide initiator prepared by the reaction of hexamethyleneimine and n-butyllithium. Agent (described in commonly owned US Pat. No. 5,496,940).

  In one or more embodiments, the functional initiator comprises a lithiated thioacetal, such as a lithiated dithiane. Lithiated thioacetals are known and include those described in US Pat. Nos. 7,153,919, 7,319,123, 7,462,677, and 7,612,144, which are incorporated herein by reference.

式中、各Ｒ^６は、独立して、水素または１価の有機基を含み、Ｒ^０は、１価の有機基を含み、ｚは、１〜約８の整数であり、およびωは、硫黄、酸素、または第三級アミノ（ＮＲ、ここでＲは、有機基である）を含む。 In one or more embodiments, the thioacetal initiator used is defined by the following formula:

Wherein each R ⁶ independently comprises hydrogen or a monovalent organic group, R ⁰ comprises a monovalent organic group, z is an integer from 1 to about 8, and ω is Contains sulfur, oxygen, or tertiary amino (NR, where R is an organic group).

式中、Ｒ^０は、１価の有機基を含む。 In one or more embodiments, the functional initiator can be defined by the formula:

In the formula, R ⁰ contains a monovalent organic group.

  Specific examples of functional initiators include 2-lithio-2-phenyl-1,3-dithiane, 2-lithio-2- (4-dimethylaminophenyl) -1,3-dithiane, and 2-lithio-2- ( 4-dibutylaminophenyl) -1,3-dithiane, 2-lithio- [4- (4-methylpiperazino)] phenyl-1,3-dithiane, 2-lithio- [2- (4-methylpiperazino)] phenyl-1 , 3-dithiane, 2-lithio- [2-morpholino] phenyl-1,3-dithiane, 2-lithio- [4-morpholin-4-yl] phenyl-1,3-dithiane, 2-lithio- [2 -Morpholin-4-yl-pyridine-3] -1,3-dithiane, 2-lithio- [6-morpholin-4-pyridino-3] -1,3-dithiane, 2-lithio- [4-methyl -3,4-dihydro 2H-1,4-benzoxazine -7] -1,3-dithiane, and mixtures thereof.

  The amount of initiator required to achieve the desired polymerization can vary depending on a number of factors such as the molecular weight of the desired polymer and the desired physical properties of the polymer being produced. Typically, the amount of initiator used can vary from as little as 0.1 g lithium per 100 g monomer to 100 g lithium per 100 mM monomer and depends on the molecular weight of the desired polymer.

  The polymerization is usually carried out in a conventional solvent for anionic polymerization such as hexane, cyclohexane and benzene. Various polymerization techniques such as a batch method, a semi-batch method and a continuous polymerization method can be used.

  Polymerization can be initiated by adding a composition comprising at least one oxolanyl compound and an initiator as described above after charging the mixture of monomer and solvent into a suitable reaction vessel. This method is performed under anhydrous and anaerobic conditions. In most cases, the process is carried out in a dry, inert gas atmosphere. The polymerization can be carried out at any convenient temperature such as −78 ° C. to 150 ° C. In batch polymerization, it is suitable to keep the peak temperature at 50 ° C to 150 ° C, and it is also suitable to keep it at 80 ° C to 130 ° C. The polymerization may be continued for various times under stirring, such as 0.15-24 hours. After the polymerization is complete, the product is stopped with a deactivator, endcap agent and / or coupling agent as described below. The terminator is added to the reaction vessel and the vessel is agitated for 0.1 hours to 4.0 hours. Termination is usually accomplished by stirring the polymer and terminator at a temperature of 20 ° C. to 120 ° C. for 0.01 hour to 1.0 hour to ensure complete reaction.

  Terminators, coupling agents, or crosslinkers may be used to stop the polymerization and further control the molecular weight, and all these chemicals are collectively referred to herein as “termination reagents”. Useful terminators, coupling agents or crosslinkers include active hydrogen compounds such as water or alcohols. Some of these reagents may impart multifunctionality to the resulting polymer. That is, the (co) polymer may have a head functional group derived from the initiator, derived from the stopping reagent, coupling agent and crosslinking agent used in the synthesis of the polymer, It may have a functional group. Useful functionalizing agents include functionalizing agents commonly used in the art.

Examples of useful stop reagents include active hydrogen compounds such as water or alcohols (eg, isopropyl alcohol and methyl alcohol); US Pat. Nos. 3,109,871, 3,135,716, 5,332,810, 5,109,907, 5,210,145, Benzophenones disclosed in US Pat. Nos. 5,227,431, 5,329,005, 5,935,893; benzaldehyde; imidazolidone; pyrrolidinone; carbodiimide; N-cyclic amide; urea; N, N-disubstituted cyclic urea; Isocyanates; Schiff bases, which are incorporated herein by reference; U.S. Pat. Nos. 4,519,431, 4,540,744, 4,603,722, 5,248,722, 5,349,024, 5,502,129, and 5,877,336 Disclosed 4,4′-bis (diethylamino) benzophenone; alkylthiothiazoline; substituted al Dimine; substituted ketimine; Michler's ketone; 1,3-dimethyl-2-imidazolidinone; 1-alkyl substituted pyrrolidinone; 1-allyl substituted pyrrolidinone; N, N-dialkylamino-benzaldehyde (dimethylaminobenzaldehyde, etc.) 1,3-dialkyl-2-imidazolidinone (such as 1,3-dimethyl-2-imidazolidinone); 1-alkyl substituted pyrrolidinone; 1-allyl substituted pyrrolidinone; tin tetrachloride; trialkyltin such as tributyltin chloride Halides, which are incorporated herein; cyclic amino compounds, such as hexamethyleneimine alkyl chlorides, disclosed in US Pat. Nos. 5,786,441, 5,916,976, and 5,552,473, which are incorporated herein by reference. U.S. Patent Application Publication No. 2006/0074 Cyclic sulfur-containing or oxygen-containing azaheterocycles disclosed in US Pat. No. 197A1, US Patent Application Publication No. 2006 / 0178467A1 and US Pat. No. 6,596,798, which are incorporated herein by reference; Boron-containing terminators disclosed in US Pat. No. 7,598,322, which is hereby incorporated by reference. Still other examples include 1- (3-bromopropyl) -2,2,5,5-tetramethyl-1 disclosed in co-pending US Patent Application Publication Nos. 2007 / 0293620A1 and 2007 / 0293620A1. Including α-halo-ω-aminoalkanes such as aza-2,5-disilacyclopentane, which are incorporated herein by reference. Other examples include N-methyl-2-pyrrolidone disclosed in U.S. Pat.Nos. 4,677,165, 5,219,942, 5,902,856, 4,616,069, 4,929,679, 5,115,035, and 6,359,167. N-substituted aminoketones including dimethylimidazolidinone (ie 1,3-dimethylethyleneurea), N-substituted thioaminoketones, N-substituted aminoaldehydes, and N-substituted thioaminoaldehydes, which are incorporated herein by reference. Carbon dioxide; and mixtures thereof. Further examples of reactive compounds include the terminating agents described in co-owned U.S. Pat.Nos. 5,521,309, 5,502,131, 5,496,940, 5,066,729, and 4,616,069, and those subjects relating to terminating agents and termination reactions Is incorporated herein by reference. Other useful termination reagents can include structural formula (R) _a ZX _b , where Z is tin or silicon. Z is optimally tin. R is alkyl having 1 to 20 carbon atoms; cyclic alkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms or aralkyl having 7 to 20 carbon atoms. For example, R may include methyl, ethyl, n-butyl, neophyll, phenyl, cyclohexyl and the like. X is a halogen such as chlorine or bromine, or alkoxy (—OR), “a” is an integer from 0 to 3, and “b” is an integer from 1 to 4, where a + b = 4. Examples of such terminators are tetraethylorthosilicate (TEOS), Si (OEt) ₄ , and methyltriphenoxysilane, MeSi (OPh) as well as tin tetrachloride, tributyltin chloride, butyltin trichloride, butylsilicon trichloride. ₃ ) included. Other reagents include those disclosed in alkoxysilane Si (OR) ₄ , RSi (OR) ₃ , R ₂ Si (OR) ₂ , (co-pending US Patent Application Publication No. 2007 / 0149744A1). Includes cyclic siloxanes (such as hexamethylcyclotrisiloxane) incorporated herein, and mixtures thereof. The organic moiety R is selected from the group consisting of alkyl having 1 to 20 carbon atoms, cycloalkyl having 3 to 20 carbon atoms, aryl having 6 to 20 carbon atoms, and aralkyl having 7 to 20 carbon atoms. Typical alkyl includes n-butyl, s-butyl, methyl, ethyl, isopropyl and the like. Cycloalkyl includes cyclohexyl, menthyl and the like. Aryl and aralkyl groups include phenyl, benzyl and the like.

  In some embodiments, the living polymer can be treated with both a coupling agent and a functionalizing agent, which serves to bind some chains and functionalize other chains. Combinations of coupling agents and functionalizing agents can be used in various molar ratios. Although the terms coupling agent and functionalizing agent are used herein, those skilled in the art will recognize that some compounds serve both functions. That is, some compounds may bind and provide polymer chains with functional groups. One skilled in the art will recognize that the ability to attach a polymer chain may depend on the amount of coupling agent reacted with the polymer chain. For example, an advantageous bond is such that the coupling agent has a one-to-one ratio between an equivalent amount of lithium to the initiator and an equivalent amount of leaving group (eg, a halogen atom) to the coupling agent. To be achieved.

  Examples of the coupling agent include metal halides, metalloid halides, alkoxysilanes, and alkoxystannanes.

In one or more embodiments, useful metal halides or metalloid halides are of formula (1) R ¹ _n M ¹ X _4-n , formula (2) M ¹ X ₄ , and formula (3) M ² X _3. In which R ¹ may be the same or different, and represents a monovalent organic group having 1 to about 20 carbon atoms, 1) and ^{M 1} in formula (2) represents a tin atom, silicon atom or germanium atom,, ^{M 2} represents a phosphorus atom, X is a halogen atom, n is an integer of from 0 to 3 Represents.

  Examples of the compound represented by formula (1) include halogenated organometallic compounds, and examples of the compounds represented by formulas (2) and (3) include metal halide compounds.

When M ¹ represents a tin atom, the compound represented by the formula (1) is, for example, triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, trihexyltin chloride, trioctyltin chloride, diphenyltin dichloride, dibutyltin dichloride. Dihexyltin dichloride, dioctyltin dichloride, phenyltin trichloride, butyltin trichloride, octyltin trichloride and the like may be used. Furthermore, tin tetrachloride, tin tetrabromide, etc. can be illustrated as a compound represented by Formula (2).

When M ¹ represents a silicon atom, the compound represented by the formula (1) is, for example, triphenylchlorosilane, trihexylchlorosilane, trioctylchlorosilane, tributylchlorosilane, trimethylchlorosilane, diphenyldichlorosilane, dihexyldichlorosilane, dioctyldi It may be chlorosilane, dibutyldichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, hexyltrichlorosilane, octyltrichlorosilane, butyltrichlorosilane, methyltrichlorosilane, and the like. Furthermore, silicon tetrachloride, silicon tetrabromide, etc. can be illustrated as a compound represented by Formula (2). When M ¹ represents a germanium atom, the compound represented by the formula (1) may be, for example, triphenyl germanium chloride, dibutyl germanium dichloride, diphenyl germanium dichloride, butyl germanium trichloride, and the like. Furthermore, germanium tetrachloride, germanium tetrabromide, etc. can be illustrated as a compound represented by Formula (2). Lintrichloride, lintribromide, etc. can be illustrated as a compound represented by Formula (3). In one or more embodiments, a mixture of metal halides and / or metalloid halides can be used.

In one or more embodiments, useful alkoxysilanes or alkoxystannanes may be selected from the group consisting of compounds of the formula (1) R ¹ _n M ¹ (OR) _4-n , wherein R ¹ may be the same or different, and represents a monovalent organic group having 1 to about 20 carbon atoms, M ¹ represents a tin atom, a silicon atom, or a germanium atom, OR represents an alkoxy group R represents a monovalent organic group, and n represents an integer of 0 to 3.

  The compound represented by the formula (4) includes tetraethylorthosilicate, tetramethylorthosilicate, tetrapropylorthosilicate, tetraethoxytin, tetramethoxytin, and tetrapropoxytin.

  The amount of terminator required to achieve the desired termination of the polymerization can vary depending on a number of factors such as the molecular weight of the desired polymer and the desired physical properties of the polymer being produced. Usually, the amount of terminator used can vary from 0.1: 5 to 0.5: 1.5 to 0.8: 1.2 (terminator: Li) in molar ratio.

  Implementation of the polymerization methods described herein can be performed by selecting other compounds that are reactive with the polymer attached to the carbon-lithium moiety to provide the desired functional groups. It is not limited to stop reagents only. In other words, the list of stop reagents described above is not construed as limiting, but rather as feasible. While stop reagents can be used, the practice of this embodiment is not limited to a particular reagent or grade of such compound.

  While it is desirable to stop to provide a functional group at the end of the polymer, it is more desirable to stop by a coupling reaction using, for example, tin tetrachloride or other coupling agents such as silicon tetrachloride or esters. . In order to maintain good processability in the subsequent production of rubber products, a high value of tin coupling is desirable. It is preferred that the polymer used in the vulcanizable elastomeric composition for this embodiment has at least 25% tin coupling. That is, for example, when measured by gel permeation chromatography, 25% of the mass of the polymer after coupling is higher than the molecular weight of the polymer before coupling. Suitably, prior to coupling, the polymer polydispersity (ratio of weight average molecular weight to number average molecular weight), which can be controlled over a wide range, is preferably less than 2 and more preferably less than 1.5. And less than 1.3 are more preferred.

  As noted above, a polydiene (co) polymer is prepared using various techniques known in the art to perform the polymerization process described herein without departing from the scope of this embodiment. be able to.

  In an additional embodiment, the polymerization process comprises a polymerization step of 1,3-butadiene in the presence of the oxolanyl compound 2,2-di (2-tetrahydrofuryl) propane, wherein the oxolanyl compound is at least 52% by weight of meso-isomerism. Including the body. Such a process produces a polydiene polymer with a vinyl content of 20-65%, involves the use of an organolithium anionic initiator and is carried out at a temperature between 85 ° C and 120 ° C.

  (Co) polymers prepared using the compositions and methods disclosed herein are particularly useful for use in preparing tire components (eg, treads and sidewalls). Such tire members can be prepared by using the (co) polymer alone or with other rubbery polymers or elastomers. Preferably, (co) polymers are used in the tread formulation, and these tread formulations are 10 to 100 weight percent (co) polymer (ie 100 parts of total rubber) based on the total rubber in the formulation. Or 10 to 100 parts of copolymer per phr). More preferably, the tread formulation contains 35-80% by weight, more preferably 50-80% by weight (co) polymer, based on the total weight of rubber in the formulation.

  Prepare a vulcanizable composition (or rubber composition) comprising a co (polymer) prepared using the compositions and methods disclosed herein and optionally one or more other rubber polymers. The at least one filler is incorporated and mixed or compounded with a rubber member comprising any other rubber polymer as well as the (co) polymers disclosed herein. May be. Other rubbery elastomers or polymers that may be used include natural and synthetic elastomers. Synthetic elastomers are usually derived from the polymerization of conjugated diene monomers. These conjugated diene monomers may be copolymerized with other monomers such as vinyl aromatic monomers. Other rubbery elastomers may be derived from the polymerization of ethylene, one or more α-olefins and any one or more diene monomers.

  Useful rubbery elastomers include, but are not limited to, natural rubber, synthetic polyisoprene, polybutadiene, polyisobutylene-co-isoprene, neoprene, poly (ethylene-co-propylene), poly (styrene-co-butadiene), poly (Styrene-co-isoprene), and poly (styrene-co-isoprene-co-butadiene), poly (isoprene-co-butadiene), poly (ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber , Urethane rubber, silicone rubber, epichlorohydrin rubber, and mixtures thereof. These elastomers may have a wide variety of polymer structures including linear, branched and star shaped. Other ingredients commonly used in rubber compounding may be added.

  The rubber composition may contain fillers such as inorganic and organic fillers. Commonly used organic fillers include carbon black and starch. Commonly used inorganic fillers include silica, aluminum hydroxide, magnesium hydroxide, clay (hydrous aluminum silicate), and mixtures thereof.

In one or more embodiments, the silica (silicon dioxide) comprises hydrous silica produced by chemical reaction in a wet process, water, and precipitates as ultrafine spherical particles. In one embodiment, the silica has a surface area of from about 32 to about 400 m ² / g, in other embodiments from about 100 to about 250 m ² / g, and in yet another embodiment from about 150 to about 220 m ² / g. . The pH of the silica filler in one embodiment is from about 5.5 to about 7, and in another embodiment from about 5.5 to about 6.8. Commercially available silicas include Hi-Sil (R) 215, Hi-Sil (R) 233, Hi-SiL (R) 255LD, and Hi-Sil (R) 190 (PPG Industries; Pittsburgh, PA). ), Zeosil (R) 1165MP and 175GRPplus (Rhodia), Vulkasil (R) (Barry AG), Ultrasil (R) VN2, VN3 (Degussa), and HuberSil (R) 8745 (Hoover).

In one or more embodiments, the carbon black may comprise any commercially available and commercially produced carbon black. These carbon blacks include carbon blacks having a surface area (EMSA) of at least 20 m ² / g, and in other embodiments at least 35 m ² / g to 200 m ² / g or more. Surface area values include those determined by ASTM Test D-1765 using the cetyltrimethylammonium bromide (CTAB) method. Useful carbon blacks are furnace black, channel black and lamp black. More specifically, examples of carbon black include super ablation furnace (SAF) black, high ablation furnace (HAF) black, high speed extrusion furnace (FEF) black, fine furnace (FF) black, intermediate super ablation furnace (ISAF). ) Black, semi-reinforced furnace (SRF) black, intermediate processing channel black, hard processing channel black and conduction channel black. Other carbon blacks that may be used include acetylene black. A mixture of two or more of the above blacks can be used. Examples of carbon black include carbon black having ASTM numbers (D-1765-82a) N-110, N-220, N-339, N-330, N-351, N-550, and N-660. . In one or more embodiments, the carbon black may include oxidized carbon black.

  In one embodiment, the silica is from about 5 to about 100 parts by weight per hundred parts rubber (phr), in other embodiments from about 10 to about 90 parts by weight phr, and in still other embodiments from about 15 to about 100 parts by weight. An amount of 80 parts by weight phr, and in still other embodiments from about 25 to about 75 parts by weight phr may be used.

  Many rubber curing agents may be used as is well known to those skilled in the art. For example, a sulfur or peroxide based curing system may be used. Also, Kirk-Othmer, ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, 3rd edition, Wiley Interscience, New York 1982, Volume 20, pages 365-468, especially VULCANIZATION AGENTS AND AUXILIARY MATERIALS 390-402, or AY Coran's Vulcanization, ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, 2nd edition, John Wiley & Sons, 1989, which are hereby incorporated by reference. Vulcanizing agents may be used alone or in combination. In one or more embodiments, the preparation of the vulcanizable composition and the tire composition and cure are unaffected.

  Other ingredients that can be used are well known to those skilled in the art, and include accelerators, oils, waxes, scorch inhibitors, processing aids, zinc oxide, adhesive resins, reinforcing resins, fatty acids such as stearic acid, peptizers, And one or more additional rubbers. Examples of oils include paraffinic oils, aromatic oils, naphthenic oils, vegetable oils other than castor oil, and low PCA oils including MES, TDAE, SRAE, heavy naphthenic oils, and black oils.

  In one or more embodiments, the vulcanizable rubber composition may be prepared by forming an initial masterbatch that includes a rubber component and a filler (the rubber component is optionally other Including polymers and rubbery polymers such as functional polymers). This initial masterbatch may be mixed at a starting temperature from about 25 ° C to about 125 ° C and a discharge temperature from about 135 ° C to about 180 ° C. This initial masterbatch may exclude vulcanizing agents to prevent premature vulcanization (also known as scorch). Once the initial masterbatch has been processed, the vulcanizing agent may be introduced and mixed with the initial masterbatch at a low temperature in the final mixing step, preferably without starting the vulcanization step. Optionally, an additional mixing step, sometimes called remilling, may be performed between the masterbatch mixing step and the final mixing step. Various components, including polymers and copolymers, can be added during these remills. The rubber compounding techniques and additives used here are generally known as disclosed in The Compounding and Vulcanization of Rubber of Rubber Technology (2nd Edition, 1973).

  Mixing conditions and methods applicable to silica filled tire formulations are also well known as described in U.S. Pat.Nos. 5,227,425, 5,719,207, 5,717,022, and EP 890,606. All of which are hereby incorporated by reference. In one or more embodiments, when silica is used as a filler (alone or in combination with other fillers), coupling agents and / or screening agents may be added to the rubber formulation during mixing. Useful coupling agents and screening agents are described in U.S. Pat.Nos. 3,842,111, 3,873,489, 3,978,103, 3,997,581, 4,002,594, 5,580,919, 5,583,245, 5,663,396, 5,674,932, 5,684,171. No. 5,684,172, No. 5,696,197, No. 6,608,145, No. 6,667,362, No. 6,579,949, No. 6,590,017, No. 6,525,118, No. 6,342,552, and No. 6,683,135. Incorporated into the book. In one embodiment, the initial masterbatch is prepared by including a rubbery polymer and / or copolymer and silica, and substantially free of coupling and shielding agents. This method is believed to increase the chance that the functional polymer will react or interact with the silica before competing with the coupling or shielding agent that can be added in a subsequent vulcanization remill.

  When vulcanizable rubber compositions are used in the manufacture of tires, these compositions can be applied to tire components by standard tire molding techniques, mold techniques and curing (vulcanization) techniques. Can be processed. Any of a variety of rubber tire members can be assembled including, but not limited to, treads, sidewalls, belt skims, and carcass. Typically, vulcanization is achieved by heating the vulcanizable composition in a mold; for example, the vulcanizable composition may be heated to about 140 ° C to about 180 ° C. Vulcanized or crosslinked rubber compositions are sometimes referred to as vulcanizates, which typically include a thermosetting three-dimensional polymer network. Other components such as processing aids and fillers may be uniformly dispersed in the vulcanized network. Pneumatic tires can be manufactured as discussed in US Pat. Nos. 5,866,171, 5,876,527, 5,931,211 and 5,971,046, which are hereby incorporated by reference.

  This application discloses several numerical range limitations, which support any range within the disclosed numerical ranges, with explicit range limitations being stated verbatim in the specification. This is not because the embodiments can be implemented over the disclosed numerical ranges. With respect to any terms that are substantially multiple and / or single herein, one of ordinary skill in the art can translate the multiple terms into a single term and / or a single term into multiple terms, And / or understand this application. Various single / plural permutations described herein may be clearly indicated for clarity.

  In general, the terms used in this specification, particularly the appended claims (eg, the appended claims text), are generally referred to as “open” terms (eg, the term “includes,” includes “ The term “having” is interpreted as “including at least”, the term “including” is interpreted as “including but not limited to”, etc .; As understood by those skilled in the art. Where a particular number is intended to be stated in an introduced claim, such intention is expressly stated in the claim, and in the absence of such a statement, it is further understood by those skilled in the art that such intention does not exist. Understood. For example, to aid understanding, the following appended claims may include use of the introductory phrases “at least one” and “one or more” to introduce claim recitations. However, the use of such phrases means that any particular claim, including a claim so introduced by the introduction of a claim recitation by the indefinite article "a" or "an", is included in that claim. An invention containing only one such enumeration, even if it contains the introductory phrases “one or more” or “at least one”, even if it contains an indefinite article such as “a” or “an” It should not be construed as limiting (eg, “a” and / or “an” are intended to mean “at least one” or “one or more”), and the same The same applies to the use of definite articles used to introduce the enumerations. Further, even if the introductory list of a particular number of claims is explicitly stated, such a statement means at least the stated number (eg, “2 One skilled in the art understands that the mere description “description” is to be interpreted as meaning at least two enumerations or more than one enumeration. Further, where conventions similar to “at least one of A, B, and C, etc.” are used, such a configuration is generally intended in the sense that those skilled in the art understand the conventions (eg, “A system having at least one of A, B, and C” means A only, B only, C only, A and B together, A and C together, B and C together, and / or Including, but not limited to, systems having both A, B, and C). Where conventions similar to “at least one of A, B, or C, etc.” are used, generally such configurations are intended in the sense that those of ordinary skill in the art understand the conventions (eg, “A , B, or C "includes only A, B only, C only, A and B together, A and C together, B and C together, and / or A, B , And a system having both C, but is not limited to these.) Substantially any disjunctive word and / or phrase that presents two or more alternative terms may be either one, the other, or both of the terms, even in the detailed description, claims, or drawings. Those of ordinary skill in the art will further understand that they are to be understood as intended to include. For example, the phrase “A or B” is understood to include the possibilities of “A”, “B”, or “A and B”.

  All documents, including but not limited to patents, patent applications, and non-patent documents, are incorporated herein in their entirety.

  While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are intended to be illustrative and not restrictive, with the true scope and spirit being indicated by the following claims.

構造は、（図３および４に示すように）１Ｈ−ＮＭＲでも確認した。図３では、メソ体を示すメチルの２つのピークに留意されたい。図４では、Ｄ，Ｌ形を示すメチルの１つのピークに留意されたい。 Isolation of diastereoisomers of 2,2-di (2-tetrahydrofuryl) propane Using commercially available amounts of 2,2-di (2-tetrahydrofuryl) propane (Penn Specialty Chemicals) using column chromatography And the diastereoisomers were isolated. A column was prepared with a 230-400 mesh size silica gel (available from Fisher Scientific) stationary phase and a mobile phase of 20% diethyl ether and 80% n-pentane. A 25 mL repetitive amount of mobile phase was used. Pure meso-2,2-di (2-tetrahydrofuryl) propane was isolated as the first fraction. The yield of the meso-isomer was about 20% of the original amount of 2,2-di (2-tetrahydrofuryl) propane. Pure D, L-2,2-di (2-tetrahydrofuryl) propane was isolated as the second fraction, and the yield was also about the same as the original amount of 2,2-di (2-tetrahydrofuryl) propane. It was 20%. GC-FID analysis of starting 2,2-di (2-tetrahydrofuryl) propane and two diastereoisomers confirmed the purity of the first two fractions. The conditions are as follows: Use Supelco's Equity 1 column (30 m × 0.32 mm × 5.0 μm); GC-injection port temperature: 260 ° C .; injection port split ratio: 20: 1; Run in constant flow mode at 5 mL / min; FID temperature: 280 ° C .; sample size: 1 μL.
Column oven program:

The structure was also confirmed by 1H-NMR (as shown in FIGS. 3 and 4). In FIG. 3, note the two peaks of methyl indicating meso form. In FIG. 4, note the single peak of methyl showing the D, L form.

A nitrogen purged 800 mL vessel equipped with a 1,3-butadiene polymerized crimp seal cap was charged with 21.8% (183.5 g) 1,3-butadiene in hexane, 1.65 M n-butyllithium in hexane. 0.24 mL and various meso, DL or commercially available 2,2-di (2-tetrahydrofuryl) propane (51 wt.% Meso isomer and about 49 wt.% D and L isomers). Various amounts of content (hereinafter "mixture") (Table 1 below) were added. The container was placed in a 50 ° C. water bath for 4 hours. The concentration of 2,2-di (2-tetrahydrofuryl) propane (“DTHF”) was measured by GC, the vinyl content was measured by ¹ H-NMR, and the molecular weight was determined by GPC using the appropriate Mark-Houwink constant. (Polystyrene standard).

The properties of the resulting polymer are listed in Table 1, and a plot of the concentration of oxolanyl compound versus% vinyl content in the resulting polybutadiene is shown in FIG. The meso form of the oxolanyl compound was more effective in producing vinyl content than the DL form mixture. In other words, a relatively small amount of meso form was required to produce the same vinyl content.

Polymerization of 1,3-butadiene and styrene A nitrogen-purged 800 mL container equipped with a crimp seal cap was charged with 23.5 g of styrene in hexane and 22.3 g of 1,3-butadiene in hexane. 14.35 g, 0.24 mL of n-butyllithium 1.65M in hexane, and various meso (100% meso), pure DL (DL 100%) or commercially available 2,2-di (2-tetrahydro Furyl) propane (containing about 50 wt.% Meso isomer and about 50 wt.% D and L isomer, hereinafter referred to as “mixture”) (Table 2 below) was added. The container was placed in a 50 ° C. water bath for 4 hours. The concentration of 2,2-di (2-tetrahydrofuryl) propane is measured by GC, the vinyl content is measured by ¹ H-NMR, and the molecular weight is determined by GPC (polystyrene standard) using the appropriate Mark-Houwink constant. It was measured.

The properties of the resulting polymer are listed in Table 2, and a plot of the concentration of oxolanyl compound versus% vinyl content in the resulting polybutadiene is shown in FIG. Again, the meso form of the oxolanyl compound was more effective in producing vinyl content than the DL form mixture. In other words, a relatively small amount of meso form was required to produce the same vinyl content.

Effect of Meso / D, L DTHFP on Vinyl in Polybutadiene Polymerization To a 800 mL container purged with nitrogen was added 214 g of hexane and 186 g of 21.5 wt% butadiene in hexane. Then about 0. 0 of various meso concentrations (99.8%, 88.1%, 87.3%, 75%, 65.3%, 54.9%, 44.9%, and 5.8%). Either 0.08 mL, 0.15 mL, 0.30 mL, 0.60 mL or 1.0 mL of 4M 2,2-ditetrahydrofurylpropane was added. Thereafter, 0.24 mL of 1.65M n-butyllithium in hexane was added and the vessel was heated to 50 ° C. for 4 hours. ¹ H-NMR was used to measure the vinyl content in the polybutadiene sample, and GC was used to measure the concentration of 2,2-ditetrahydrofurylpropane.

The resulting polymer properties are listed in Table 3 and a plot of vinyl content as a function of ppm DTHP at various meso DTHF concentrations is shown in FIG.

Next, the rate of anionic butadiene polymerization was improved in the presence of 99.8% meso 2,2-ditetrahydrofurylpropane and 49.7% meso 2,2-ditetrahydrofurylpropane. The polymerization carried out was investigated.

Butadiene polymerization rate using 99.8% 2,2- ditetrahydrofurylpropane meso: A nitrogen purged 7.57 L stainless steel reactor with 0.54 kg anhydrous hexane and 20.9 wt% 1,3 in hexane -1.63 kg of butadiene was added. Then 0.33 M 2,2-ditetrahydrofurylpropane (meso 99.8%) 5.73 mL and 1.65 M butyllithium 1.37 mL in hexane were added at 11.7 ° C. The reactor jacket was set to 71.1 ° C. (Meso 99.8% 2,2-ditetrahydrofurylpropane was isolated using the column chromatography method described above). Samples at 5, 10, 15, 20, 25, 30, 45, 60, and 90 minutes were taken to measure conversion and molecular weight. The vinyl content of the samples at 20, 30 and 60 minutes was examined by ¹ H-NMR. The concentration of 1,3-butadiene and 2,2-ditetrahydrofurylpropane (124 ppm) in the reaction was measured using GC.

For the samples taken at the indicated reaction times, the resulting polymer properties are listed in Table 4 and the plots show the butadiene weight percent of the reaction mixture over time and the temperature of the reaction mixture over time. Is shown in FIG. The weight percentage of butadiene in the reaction mixture over time was plotted with a dashed line in FIG. 6, and the temperature of the reaction mixture over time was plotted with a solid line in FIG.

Butadiene polymerization rate using 49.7% meso 2,2- ditetrahydrofurylpropane Nitrogen purged 7.57 L stainless steel reactor with 0.54 kg anhydrous hexane and 20.9 wt% 1,3 in hexane -1.63 kg of butadiene was added. Then 0.82 mL of 1.6 M 2,2-ditetrahydrofurylpropane (meso 49.7%) and 1.37 mL of 1.65 M butyllithium in hexane were added at 12.1 ° C. (The 49.7% meso 2,2-ditetrahydrofurylpropane received from the supplier was used.) The reactor jacket was set to 71.1 ° C. Samples at 5, 10, 15, 20, 25, 30, 45, 60, and 90 minutes were taken to measure the polymerization rate and molecular weight. The vinyl content of the samples at 20, 30 and 60 minutes was examined by ¹ H-NMR. The concentration of 1,3-butadiene and 2,2-ditetrahydrofurylpropane (176 ppm) in the reaction was measured using GC.

実施例は、ＤＴＨＦＰ濃度が一定でメソ含有量が増加すると、結果物の重合体のビニル含有量が増加することを示している。最後の２つの実施例は、メソ９９．８％のＤＴＨＦＰ（１２４ｐｐｍ）の約６０％を用いた反応器による実行が、メソ５０％までのＤＴＨＦＰ（１７６ｐｐｍ）の１００％を用いた場合と同様のビニル含有量を与えることを示している。 The resulting polymer properties are listed in Table 5 and a plot showing the weight percent of butadiene in the reaction mixture over time and the temperature of the reaction mixture over time is shown in FIG. The weight percentage of butadiene in the reaction mixture over time was plotted with a dashed line in FIG. 6, and the temperature of the reaction mixture over time was plotted with a solid line in FIG.

The examples show that as the DTHP concentration is constant and the meso content increases, the vinyl content of the resulting polymer increases. The last two examples are similar to a reactor run with about 60% meso 99.8% DTHP (124 ppm) using 100% meso 50% DTHF (176 ppm). It gives the vinyl content.

Claims (25)

A composition comprising at least one oxolanyl compound selected from the following group:

Wherein R ₁ and R ₂ are independently hydrogen or an alkyl group, and the total number of carbon atoms in —CR ₁ R ₂ — is 1-9; R ₃ , R ₄ and R ₅ are is independently -H or _-C n _{H 2n + 1,} a n = 1 to 6, and said composition comprises meso least one oxolanyl compound - containing isomers at least 52% by weight.   The composition of claim 1, wherein the meso-isomer comprises at least 60% by weight of at least one oxolanyl compound.   The composition of claim 1, wherein the meso-isomer comprises at least 90% by weight of at least one oxolanyl compound.   The composition of claim 1, wherein the oxolanyl compound comprises 2,2-di (2-tetrahydrofuryl) propane.   The composition of claim 1, wherein the composition is a purified mixture. A polymerization method comprising the step of polymerizing at least one conjugated diene monomer in the presence of a composition comprising at least one oxolanyl compound selected from the following group:

Wherein R ₁ and R ₂ are independently hydrogen or an alkyl group, and the total number of carbon atoms in —CR ₁ R ₂ — is 1-9; R ₃ , R ₄ and R ₅ are Independently, —H or —C _n H _{2n + 1} , n = 1 to 6, and the composition comprises at least 52% by weight of the meso-isomer of at least one oxolanyl compound, the method comprising: A polydiene polymer is produced.   The method of claim 6, wherein the meso-isomer is at least 60% by weight of the composition.   The method of claim 6, wherein the meso-isomer is at least 90% by weight of the composition.   The method of claim 6, wherein the oxolanyl compound comprises 2,2-di (2-tetrahydrofuryl) propane.   The method of claim 9, wherein the meso-isomer is at least 90% by weight of the composition.   The method of claim 6, further comprising the step of polymerizing at least one vinyl aromatic monomer.   The method of claim 11, wherein the at least one vinyl aromatic monomer is selected from the group consisting of styrene, α-methyl styrene, p-methyl styrene, vinyl naphthalene, and mixtures thereof.   The at least one conjugated diene monomer is 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene, 2-methyl-1,3- Consists of pentadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, phenyl-1,3-butadiene, and mixtures thereof The method of claim 11, wherein the method is selected from the group.   The method according to claim 11, wherein the resultant polydiene polymer is a block copolymer having a vinyl content of 10% or more and less than 100%.   The method of claim 6 further comprising the use of at least one organometallic anionic initiator.   16. The method of claim 15, wherein the at least one organometallic anionic initiator is selected from the group consisting of organolithium, organomagnesium, organosodium, organopotassium, triorganotin lithium compounds, and mixtures thereof. .   The method of claim 6 further comprising the use of at least one stop reagent.   The at least one conjugated diene monomer is 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene, 2-methyl-1,3- Consists of pentadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, phenyl-1,3-butadiene, and mixtures thereof The method of claim 6, wherein the method is selected from the group.   The method of claim 6, wherein the molar ratio of the meso-isomer to the organometallic anionic initiator is 0.001: 1 to 1: 1.   A polydiene polymer or copolymer prepared by the method of claim 6.   A tire product comprising a polydiene polymer or copolymer prepared by the method of claim 6. A polymerization method comprising a step of polymerizing 1,3-butadiene in the presence of an oxolanyl compound 2,2-di (2-tetrahydrofuryl) propane, wherein the oxolanyl compound comprises at least 52% by weight of a meso-isomer. Including
The method produces a polydiene polymer having a vinyl content of 10 to 65%,
A polymerization method wherein the method comprises the use of an organolithium anionic initiator and the polymerization method is carried out at a peak polymerization temperature of 85 ° C to 120 ° C.   The polymerization method according to claim 22, wherein the method further comprises a step of polymerizing styrene and 1,3-butadiene to produce a copolymer.   The polymerization method of claim 22 further comprising the use of at least one stop reagent.   23. A tire product comprising a polydiene polymer or copolymer prepared by the method of claim 22.

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